Pesticidal bis-pyridyl amine derivatives

ABSTRACT

Pesticidal compositions containing bis-pyridyl amine derivatives and methods of using the same.

United States Patent 1 Barlow et al.

[ Dec. 30, 1975 [54] PESTICIDAL BIS-PYRIDYL AMINE DERIVATIVES [75] Inventors: Charles Brian Barlow, Camberley;

Clive Dudley Spencer Tomlin, Maidenhead, both of England [73] Assignee: Imperial Chemical Industries Limited, London, England [22] Filed: May 13, 1974 [2l] App]. No.: 469,599

Related U.S. Application Data [62] Division of Ser. No. 164,082, July 19, 1971, Pat.-No.

[30] Foreign Application Priority Data Aug. 4, 1970 United Kingdom 37585/70 [52] U.S. Cl 424/263; 71/94; 260/296 R; 424/226 [51] Int. Cl. AOIN 9/22 [58] Field of Search 260/296 R; 424/263 [56] References Cited UNITED STATES PATENTS 3,364,223 1/1968 Johnston 424/263 3,375,257 3/1968 Thiele 6t 31.. 260/295 3,674,877 7/1972 Freeman 424/263 3,819,558 6/1974 Ruetman 424/263 3,830,822 8/1974 Barlow 6! a] 260/296 R Primary ExaminerV. D. Turner Attorney, Agent, or FirmCushman, Darby & Cushman [57] ABSTRACT Pesticidal compositions containing bis-pyridyl amine derivatives and methods of using the same.

9 Claims, No Drawings PESTICIDAL BIS-PYRIDYL' AM-INE DERIVATIVES This is a division, of application Ser. No. 164,082 filed July 19, 1971 now US. Pat. No. 3,830,822.

This invention relates to-new compounds, to processes for obtaining them, to compositions comprising them, and to methods of combating pests using them. Accordingly this invention provides compounds having the general formula:

wherein R represents an atom of hydrogen, an unsubstituted or substituted hydrocarbon group or an acyl group; W, W, X, X, Y, Y, Z and Z represent atoms of hydrogen or halogen, or cyano, azido, hydroxy, nitro, nitroso, thiocyano, or perhalocarbyl groups,-or unsubstituted, or substituted, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amino, acyloxy, hydrocarbylcarbonyl or hydrocarbylsuphonyl groups, or. a carboxylic or sulphur-containing acid group or a salt, atnide or ester derived therefrom; provided that not more than three of W, W, X, X, Y, Y, Z and Z are atoms of hydrogen; and N-oxides of such compounds.

In a preferred aspect the invention provides compounds having the general formula:

wherein R represents an atom of hydrogen, an unsubstitutedor substituted hydrocarbon group or-an acyl group; W, W, X, X, Y, Y, Z and Z represent atoms of hydrogen or halogen, or cyano, azido, hydroxy, nitro, nitroso, thiocyano, or perhalocarbyl groups, or unsubstituted, or substituted, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amino, acyloxy, hydrocarbylcarbonyl or hydrocarbylsulphonyl groups, or a carboxylic or sulphur-containing acid group or a salt, amide or ester derived therefrom; provided that not more than three of W, W, X, X, Y, Y, Z and Z are atoms of hydrogen.

In a more preferred aspect the invention provides compounds having the formula:

wherein R represents a hydrogen atom or an alkyl group; W, W, X, X, Y, Y, Z and Z represent atoms of hydrogen or halogen, or cyano, azido, nitro, perhaloalkyl, alkoxy, aralkoxy, aryloxy, alkoxyalkoxy, alkylthio, arylthio, alkylamino, alkanesulphonyl, carboxylic acid, carboxylic ester, or carboxamide groups;

wherein R represents a hydrogen atom or a methyl group; W, W, X, X, Y, Y, Z and Z represent atoms of hydrogen, fluorine, chlorine or bromine, or cyano,

nitro, azido, trifluoromethyl, alkoxy containing up to 8 ,carbon atoms, benzyloxy, phenoxy, ethoxyethoxy,

methylthio, phenylthio, methylamino, ethylamino, dimethylamino, methanesulphonyl, carboxylic acid, carboxylic acid methyl ester or carboxamide groups; provided that not more than three of W, W, X, X, Y, Y, Z and Z are atoms of hydrogen; and N-oxides of such compounds.

In an even yet more preferred aspect the invention provides compounds having the formula:

Y Z Y wherein R represents an atom of hydrogen, an alkyl group or an acyl group; and W, W, X, X, Y, Y, Z and Z represent alkoxy, cyano, nitro, or haloalkyl groups, or atoms of hydrogen, chlorine or fluorine, provided that at least one of W, W, X, X, Y, Y, Z and Z represents an alkoxy, cyano, nitro, or haloalkyl group, and that at least four of the remaining substituents are atoms of chlorine or fluorine.

Particularly useful compounds are those comprising halogen atoms and electron donating groups as substituents. In a further aspect therefore the invention provides compounds having the general formula:

wherein R represents an atom of hydrogen, an unsubstituted or substituted hydrocarbon group or an acyl group; W, W, X, X, Y, Y, Z and Z represent atoms of hydrogen or halogen, or electron donating groups provided that at least one of W, W, X, X, Y, Y, Z and Z is an electron donating group and at least four of the remaining substituents are atoms of halogen.

The termfelectron donating group as used in this specification includes, for example, hydrocarbyl groups, hydrocarbyloxy groups, hydrocarbylthio groups, and unsubstituted and substituted amino groups.

' in an especially preferred aspect the invention provides compounds having the formula:

wherein one of W,;.W,, X, X, Y, Y, Z and Z represents a methoxy group and the remainder represent atoms of fluorine or chlorine.

5 Compounds according to the invention are those whose structural formulae are believed to be those given in Table 1 below, together with a physical characteristic for each compound.

TABLE I Compond Physical NO S'ruC'ural Formula ChOI'GC'Ol'iS H F Cl Cl F I N s N m.pl 125-l27c F cl c ocH F U F 2 N N N m.p 124.s 126.1c

F Cl c| C2H5 F Cl Cl F 3 N m.p. 1015- IDS-6C F cl oc'H F Cl Cl F N N N m.p. 7o-0-73-5c F Cl cl ocmcn Cl F 5 N m.p. 66.2-68.2c

c OC4H9(") F F F F 6 N/ N \N m.p. 7s-9-771c F ocH 7 N N m p 77-7-7a.sc

F 0c H TABLE 1 Id com Structural Fo F H c Cl N TABLE 1 corn 'd Phyucul Charuchrisliz Slrvdurul Formula Compound No Imp. I51 "c limp. 1609c Imp- 75- 2C Imp. 183C TABLE 3 cont d Compound 0 Phys ic cl No. S ruc'ural Formal? chum".risfic L. I06.2 C 0 mmi 11a.2

42 N p "up. 123% 44 m. .,l 06C 5 Imp. 152 C F C] F F 46 N N N Imp, 110-0;

H no.9 c F C] F F F C] 47 N N Im 2oac TABLE I com d Compound Physi cal No. s'ruc'uml Formula Churuc'oristic ss P- 350? It should be noted that for each of the compounds of Table 1, except compound 13, the formula given is one of a number of tautomeric possibilities. Thus compounds of the general formula: etc.

I\ W 1 N Where the nature of a substituent allows it the 'tautoa meric possibilities are even further increased. The pres- 1 ent invention is to be considered as including within its Y z Z Y scope all tautomeric forms of the invention compounds. may also be represented by other tautomerically re- Another possibility with some of the azido substilat d f rmul tuted compounds of the present invention is that the including, for example, the following: structures of the compounds may be represented as tetrazolepyridines. Thus, for example, compound no. x W 1 i1 22 of Table I, may be represented as having the isow meric structural formula:

\ N NH 2 1 c1 u --N Y Z Z N J 65 or a tautomeric form thereof, and the present invention includes within its scope all such isomeric and mummeric forms.

A particularly useful compound pesticidally is 3,3,5-

x w W1 Y z z ing the formula:

I Y sa it z with a base, and then reacting the treated compound thus produced with a compound of the formula:

Hal

wherein W, W, X, X, Y, Y, Z, and Z have any of the meanings hereinbefore defined and Hal represents an atom of' halogen. A suitable base for use in the above reaction is sodium hydride, and the process may be carried out in a'diluent or solvent, for example dimethylformamide. Many of the reactants used in the above process are themselves novel compounds, and have not been previously described in the literature.

In a further aspect therefore the invention provides compounds having the formula:

2 Hulk n. I an u where each Hal separately represents fluorine or chlorine arid-R isan unsubstituted, or substituted, hydrocarbyloxy, hydrocarbylthio or amino group. These compounds may be obtained by treating the corresponding tetrahalopyridylamine with a compound RH, optionally in the presence of a base.

In particular, the invention provides the compound having the formula:

l r ocu which has utility as a reactant in the preparation of certain of the invention compounds as hereinbefore defined.

This reactant may be prepared by treating the compound having the formula:

with a methanolic solution of sodium methoxide.

The compounds of the invention may be used as pesticides either on their own or, preferably, incorporated in a composition comprising a diluent in addition to the invention compound.

The invention, therefore, further provides pesticidal compositions, comprising as an active ingredient a compound having the formula:

wherein R, W, W, X, X", Y, Y, Z and Z have any of the meanings as hereinbefore defined.

In a preferred aspect the invention provides pesticidal compositions comprising as an active ingredient any of the compounds given in Table l.

Compounds of the invention and compositions comprising them are very toxic towards insect and other invertibrate pests, including for example the following:

Tetranychus telarius Plutella maculipennis Aphis fabae Pieris brassicae Blattella germanica Megoura viciae Phaedon cochleariae Musca domestica Aedes aegypti Agriolimax reticulatus Meloidogyne incognita Calandra granaria Baophilus spp.

(red spider mites) (diamond back moth) (black aphids) (cabbage white caterpiller) (cockroaches) (green aphids) (mustardbeetle) (houseflies) (mosquitos) (greyfield slug) (nematodes) (grain weevils) (cattle ticks) Thecompounds of the invention, and compositions comprising them,'possess activity against a wide variety of plant foliar and post-harvest fungal and bacterial diseases including, for example, the following specific diseases? Sphaerotheca fuliginea Puccinia recondila Botrytis cinerea Phytophthora infeslans (powdery mildew) (rust) (chocolate spot) (late blight) on cucumber on tomatoes on broad beans on broad beans Podosphaera leucotricha (powdery mildew) on apple Uncinula necator (powdery mildew) on vine Piricularia oryzae (blast) on rice Plnsmopara viticola (downy mildew) on vine Venturia inaequalis (scab) on apple Bolrytis lulipae (tire) on bulbs Nigrospora sphaerica (squirter) on bananas Phomopsis citri (scab) on citrus AItemaria vim (end rot) on citrus Phylophthora citrophlhara (brown rot) on citrus Penicillium digilatum (green mould) on citrus Gloeosporium musarum (black end) on bananas Fusarium caeruleum (dry rot) on potatoes Barrodipeodia theobromae (stalk rot) on bananas Ceratocyrtir paraa'axa (gangrene) on potatoes Phoma exigus (rot) on pineapple Phlophlhora parasilica (grey mould) on citrus Xanthomonas oryzae (bacterial leaf blight) on rice Xanthomonas malvacearum (black-arm) on cotton Erwinia amylovara (fire blight) on pears and apples Erwinia carotovora (bacterial soft rot) of vegetables Pseudamonas phaseolicola (halo blight) on beans Pseudomnnar syringae (dieback) of stone fruit Pseudomanas mora-prunocrum (bacterial canker) of stone fruit (bacterial canker) (scab) (crown gall) on potatoes The invention compounds also display herbicidal 25 may be, for example kaolinite (china clay),montmorilactivity and are preferably used at higher rates of application for this purpose. The compounds are also algicidal.

In use, the invention compounds, or compositions containing them, may be used to combat pests in a variety of ways. Thus the pests themselves, or the locus of the pests, or the pest habitat may be treated to control the pests.

In a further feature therefore the invention provides a method of combating pests wherein the pests, the locus of the pests, or the habitat of the pests is treated with a compound or a composition according to the invention.

The invention alsoprovides a method of 'treating plants with-a compound or composition according to the invention to render them less susceptible to:damage by pests, which may already be occurring (i.e. treat: ment to eradicate an infestation or infection) orwhich are expected to occur (i.e. treatment to protect the plant from an infestation or infection).

In a yet further feature, therefore, the invention provides a method of treating plants to render them less susceptible to damage by pests, which comprises treating the plants, or the seeds, corms, bulbs, tubers, rhizomes or other propagative parts of the plants, with a compound or composition according to the invention.

If desired the medium in which the plants are growing may be similarly treated with a compound or composition according to the invention. 7

In another feature, therefore the invention provides a method of treating a medium in which plants are growing or to be grown which comprises applying to the medium a compound or composition according to the invention. I

The compounds and compositions of the invention may be used for agricultural or horticultural purposes and the compound or type of composition usedin any instance will depend upon the particular, purposefor which it is to be used.

Compositions comprising the invention compounds may be in the form of dusting powders or granules wherein the active ingredient is mixed with a solid diluent or carrier. Suitable solid diluents or carriers lonite, attapulgite, talc, pumic, silica, calcium carbonate, gypsum, powdered magnesia, Fullers earth, Hewitts earth and diatomaceous earth. Compositions for dressing seed, for example, may comprise an agent assisting the adhesion of the composition to the seed, for example, a mineral oil. I

The composition may also be in the form of dispersible powders or grains comprising, in addition to the active ingredient, a wetting agent to facilitate the dispersion of the powder or grains in liquids. Such powders or grains may include fillers, suspending agents and the like.

The compositions may also be in the form of liquid preparations to be usedas dips or sprays which are generally aqueous dispersions or emulsions containing the active'ingredie'nt in the presence of one or more wetting agents'jdispersing agents, emulsifyingagents or suspending agents. 7 i

Wetting agents'f'dispersing agents and emulsifying agents may be'of the cationic, anionic, or non-ionic type. S uitable'ag'ents of the cationic'type include, for example, quaternary ammonium compounds, for-example cetyltrimethylammonium bromide. Suitable agents of the anionic type include, for example, soaps, salts of aliphatic monoesters of sulphuric acid, for example sodium lauryl sulphate, salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium calcium, or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyland triisopropylnaphthalene sulphonic acids.

Suitable agents of the non-ionic type include, for example, the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octylphenoLnonylphenol and octylcresol. other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydride s,;-t,he condensation products of the said partial esters with ethylene oxide, the lecithins, and block copolymers of ethylene oxide and propylene oxide.

Suitable suspending agents are, for example, bentonite, pyrogenic silica, and hydrophilic colloids, for example polyvinylpyrrolidone and sodium carboxymethylcellulose, and the vegetable gums, for example gum acacia and gum tragacanth.

The aqueous solutions dispersions or emulsions may be prepared by dissolving the active ingredient or ingredients in an organic solvent which may contain one or more wetting, dispersing or emulsifying agents and then adding the mixture so obtained to water which may likewise contain one or more wetting, dispersing or emulsifying agents. Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes and trichloroethylene.

The compounds of the invention may also be formulated into compositions comprising capsules or microcapsules containing either the active ingredient itself, or a composition containing the active ingredient, and prepared by any of the known encapsulation or microencapsulation techniques.

The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant such as fluorotrichloromethane or dichlorodifluoromethane.

By the inclusion of suitable additives, for example, for improving the distribution, adhesive power and resistance to rain on treated surfaces, the different compositions can be better adapted for the various uses for which they are intended.

The compounds of this invention may also be conveniently formulated by admixing them with fertilizers. A preferred composition of this type comprises granules of fertilizer material incorporating, for example coated with, a compound of the invention. The fertilizer material may, for example, comprise nitrogen or phosphatecontaining substances.

In yet a further aspect of the invention, therefore, we provide a pesticidal composition comprising as an ac- 'tive ingredient a compound of the invention in admixture with a fertilizer material.

The compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient or ingredients, the said concentrate to be diluted with water before use.

These concentrates are often required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain from 1085% by weight of the active ingredient or ingredients and generally from 25-60% by weight of the active ingredient or ingredients. When diluted to form aqueous preparations, such preparations may contain varying amounts of the active ingredients or ingredients depending upon the purpose for which they are to be used, but an aqueous preparation containing between 0.0001 and 1.0% by weight of the active ingredient or ingredients may be used.

It is to be understood that the pesticidal compositions of this invention may comprise, in addition to a compound of the invention, one or more other compounds having biological activity.

The invention is illustrated, but not limited, by the following examples.

EXAMPLE 1 This example illustrates the preparation of 4-amino- 3,5-dichloro-2-fluoro-6-methoxypyridine, having the formula:-

Z C1 C 1? H CH 4-amino-3,5-dichloro-2,6-difluoropyridine (4.98 g.) was dissolved in methanol at 18C., and a solution of sodium methoxide (prepared by dissolving sodium (0.576 g.) in methanol (25 cc.) added dropwise with stirring. The reaction mixture was then heated to reflux for two hours, after which time it was cooled and poured into excess distilled water. The precipitated product was collected by filtration and recrystallised from petroleum ether (boiling range 60 to C.) to yield 4-amino-3,5-dichlore-2-fluoro-6-methoxypyridine, having a melting point of lO7.9 to 108.3C.

EXAMPLE 2 By a procedure similar to that illustrated in Example 1, but using the appropriate reactants the following compounds were prepared:-

4-amino-3,5-dich1oro-2-fluoro-6-ethoxypyridine (m.p. 8082C) 4-amino-3,5-dichloro-2-fluoro-6-n-propoxypyridine (m.p. 5455.5C) 4-amino-3,5-dichloro-2-fluoro-6-isopropoxypyridine (m.p. 74C) 4-amino-3,5-dich1oro-2-fluoro-6-n-butoxypyridine (m.p. 47.3-49.4C)

4-amino-2,3,5-trifluoro-6-methoxypyridine (m.p.

4-amino-2,3,5-trifluoro-6-ethoxypyridine (m.p.

4-amino-2,3 ,5-trich1oro-6-methoxypyridine (m.p.

4-amino-2,3,5-trichloro-6-ethoxypyridine (m.p.

EXAMPLE 3 This example illustrates the preparation of 4-amino- 3,5-dichloro-6-fluoro-2-methylthiopyridine, having the formula:-

27 4-Amino-3,5-dichloro-2,6-difluoropyridine (19.9 g) was dissolved in 1,4-dioxane (300 cc) and sodium hydroxide (2N, 50 cc) was added to the solution. Gaseous methyl mercaptan was gently bubbled through the mixture and during the addition the temperature was slowly increased until refluxing occurred. The gas flow was continued until no starting material could be detected by thin layer chromatography on alumina using chloroform eluent. The mixture was evaporated under reduced pressure and the residue treated with water (100 cc.) to yield a white precipitate which was collected by filtration and recrystallised from petroleum ether (boiling range 6080C). The 4-amino-3,5- dichloro-6-fluoro-2-methylthiopyridine thus obtained has a melting point of 99 to 100C.

EXAMPLE 4 By an analogous procedure to that illustrated in Example 3, but using the appropriate amines or thiols in place of methyl mercaptan the following compounds were prepared:-

4-amino-2,3,5-trichloro-6-dimethylaminopyridine (m.p. 69C) 4-amino-3,5-dichloro-2-fluoro-6-dimethylaminopyridine (m.p. 85-86.6C) 4-amino-3,5-dichloro-2-fluoro-6-methylaminopyridine (m.p. 144-145C) 4-amino-3,5-dichloro-2-fluoro-6-phenylthiopyridine (m.p. 107-108C) 4-amino-3,5-dichloro-2-fluoro-6-ethylaminopyridine 3 (mp. l08-l09C) EXAMPLE 5 This Example illustrates the preparation of 4-amino- 3,5-dichloro-2,6-diazidopyridine having the formula:-

EXAMPLE 6 This example illustrates the preparation of 4-amino- 2,3,5-trichloropyridine having the formula:-

2,3,4,5-tetrachloropyridine (15 g) concentrated ammonium hydroxide (5.6. 0.880; 5.16 cc.) and ethanol (30 cc) was heated for 4.5 hours at 135C in a sealed tantalum tube. The pale yellow liquid obtained was evaporated under reduced pressure at room temperature, and the residue extracted with ether. The extracts were washed with water, and then dried over anhydrous magnesium sulphate. Evaporation under reduced pressure yielded a white crystalline solid which was washed with cold petroleum ether (boiling range 30 to 40C) and recrystallised from petroleum ether (boiling range 6080C) to yield 4-amino-2,3,5-trichloropyridine, having a melting point of 148.7l49.3C.

The halopyridines and other halogenated aminopyridines and cyanopyridines used as intermediates in the preparation of the invention compounds were prepared by the methods described in the literature, e.g. West German Offenlegungsschrift 1,816,685, Banks et al, J. Chem. Soc. (C), 1967, 2089-91, or British Patent Specification, Serial No. 1,161,492. 3-Cyano-2,4,5,6-tetrafluoropyridine (b.p. 164l65) is a new compound, prepared by refluxing 3-cyanotetrachloropyridine with anhydrous potassium fluoride in sulpholane.

EXAMPLE 7 This example illustrates the preparation of 4-amino- 3,5-dichloro-6-fluoro-2-methanesulphonylpyridine having the formula:-

SO 0H} EXAMPLE 8 This example illustrates the preparation of 4-amino- 3,5 6-trichloro-2-trifluoromethylpyridine having the formula:-

k" cr 4-Amino-2-carboxy-3,5,6-trichloropyridine (7.3 g) was heated in an autoclave at C with hydrogen fluoride (4.0 g) and sulphur tetrafluoride (8.0 g) for 8 hours. The resulting dark green liquid was evaporated to dryness and the residue treated with 10% w/v aqueous sodium hydroxide solution. The mixture was extracted with chloroform and the extracts dried over anhydrous sodium sulphate and evaporated under reduced pressure. The residual s'olid wa'srpurified by recrystallization from'aqueous ethanol to yield -4'-'amino-"3,5;6-trichloi'oat 1 point This exampl illusti' a'tes the preparation of 3,3',5,5'-

C Cl

4-amino-3,5-dichlord-2-fluoro-6-m'ethoxypyridine (3.17g.) was diss'olved'in dry dimethylfo'rmamide-(20 cc.) and the solution added '-to' a stirred suspension of sodium hydride (0.72 g'.) ini dry dim'e'thylfor mamide (15 cc.), under a nitrogen atmosphere at a tempt'ature of C. When the addition wascompleteand evolution of hydrogen had ceased, a solution of 3,5-dichloro- 2,4,6-trifluoropyridine (3.03" g.) in dry dimethylformamide cc.) was added dropwise to the mixture. Some effervescence was observed during the addition, and when addition was complete the mixture --was stirred for a further 2 hours, thetemperature of the mixture being allowed. to rise during this. period to 18C. The mixture was then poured onto ice, the resultant mixture acidified with dilute hydrochloric acid, and extracted with ether. The ether extracts were then washed with water, dried over sodium sulphate and evaporated. The residual solid obtained was recrystallised from petroleum ether (boiling range 60 to 80C.) toyield 3,3-5,5-tetrachloro-2,2',6 trifluoro-6'- methoxy-4,4' -bispyridylamine, having a melting'point of"125-127C.

' EXAMPLE 10 This example illustrates the preparation of bis (3,5- I

dich1oro2,6-difluoro-4-pyridyl) amine, having the formulaz- Under an atmosphere of dry nitrogen, a suspension of 50% sodium hydride dispersion in mineral oil (4.6 g. 0.1M) (washed'with dry petroleum ether) in dry dimethyl formamide (25 ml.) was treated dropwise with k 'difluoro;4,4'-di-pyridylamine (Compound No. "Table 1", 1.0 g.) wasrefluxed with 10% (w/v) sodium being kept below 30: andthe' reaction mixture was poured into .water (.200 m1.). v

. The solution was then acidified to pH Zwith concentrated hydrochloric acid;a nd the resultingoil extracted with chloroform. After drying removal of solvent, and recrystallising the solid residue from cyclohexane, recrystallisation from 50% aqueous ethanol gave the product as white crystals of m.p. 12 3124.3.

EXAMPLE 11 By a procedure similar to those given in Examples 9 and 10 but using the appropriate reactants the compounds numbered 2 to 49, 51, 52, 54, 57 to 61 in Table 1 were prepared.

I v [EXAMPLE 12 This example'illustrates the preparation of Z-carbamoy1-3,3,5,5,'6-pentachloro-2,6.-difluoro-4,4-

dipyridylamine (compound No. 53, Table 1), having the formula:-

EXAMPLE 13 This example illustrates the preparation of 2-carboxy-3,3,5,5',6-pentachloro-2,6'-difluoro-4,4fdiphenylamine (Compound No. 50 of Table I) having the formula:

Z-Methoxycarbonyl-3 ,3 ,5 ,5 ,6-pentachloro-2 ',6-

hydroxide solution (25 cc.) for 30 minutes after which the mixture was acidified with hydrochloric acid. The oil which precipitated was collected by extraction with ethylacetate and the extracts, after drying over anhydrous sulphate, were evaporated under reduced pressure. The residual solid was recrystallised from aqueous methanol to yield 2-carboxy--3,3",5,5',6-pentach1oro- 2,6-difluoro-4,4'-dipyridylamine,.1melting with decomposition at 21021 1C;

dipyridylamine, and evaporating the mixture to dry-' ness. The resulting solid residue was recrystallised from a mixture of ethanol and petroleum ether to give the pure potassium salt. Compounds 56, 62 and 63 were also prepared and purified by a similarprocess.

EXAMPLE The activity of a number of the compounds was tested against a variety (if insect and other invertibrate pests. The compound were used in'the form of a liquid preparation containing 0.1% by weight of the compound escept in the tests with .Aedes. aegypti and Meloidogyne incognita where the preparations contained 0.01% by weight of the compound. The preparations were made by dissolving each of the compounds in a mixture of solvents consisting of 4 parts by volume of acetone and 1 part by volume of diacetone alcohol. The solutions were then diluted with water containing 0.01% by weight of a wetting agent sold under the trade name LISSAPOL NX until the liquid preparations contained the required concentration of the compound. LISSAPOL is a registered Trade Mark.

The test procedure adopted with regard to each pest was basically the same and comprised supporting a number of the pests on a medium which was usually a host plant or a foodstuff on which the pests feed, and treating either or both the pests and the medium with the preparations. v v y The mortality of the pests was then assessed at periods usually varying from 1 to 3 days after the treatment.

The results of the tests are given below in Table 2. In this table the first column indicates the name of the pest species. Each of the subsequent columns indicates the host plant or medium on which it was supported, the number of days which were allowed to elapse after the treatment before assessing the mortality of the pests, and the results obtained for each of the compounds, numbered as in Table l above. The assessment is expressed in integers which range from 0-3.

0 represents less than kill 1 represents 30-49% kill 2 represents 50-90% kill,

3 represents'over90% lcill A dash in Table 2 indicates that no test was carried out.

TABLE 2 No. No. of Compound (Table 'I) Support of v V I Pest Species Medium days l -2 3. 4 5 6 7 8 9 10 ll l2 l3 l4 l5 l6 l7 l8 19 20 2t 22 Telranychux lelarius French (red spider mites. bean 3 3 3 3 3 3 3 3 2 3 3 0 3 l 3 3 3 2 0 3 3 3 3 adults) Tetranychus lelan'us French (red spider mites, bean 3 0 3 3 3 0 0 0 3 0 0 0 3 0 0 3 l 0 0 0 3 3 0 e s) Afia his fabae Broad (green aphids) bean 2 2 3 1 3 2 0 0 0 0 0 0 0 2 0 2 0 0 0 0 3 2 Megoura viceae Broad (black aphids) bean 2 0 3 '0 3 3 0 0 0 0 0 0 0 0 I 0 0 0 0 0 0 3 0 Aedes aegypti (mosquito larvae) Water I 3 l 0 3 3 0 3 3 3 0 0 0 0- 3 3 -3 0 0 0 2 0 Aedes aegypli T a (mosquito adults) Plywood l 3 3 2 3 2 3 3 0 .0 0 0 0 0. 3 0 2. 0. ,0 v 0 0 '0 2 Musca domeslica Mllk/ (housefliessugar 2 0 3, 3 3 3 3 ,3 0 3 2 2' 3 0 3 0 0 l l 0' 0 I 3 contact test) Muscd domestica (houseflies res- Plywood 2 0 l 0 .2 0 l 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 idual test) Pieris brassicae (cabbage white Cabbage 2 2 3 0 0 3 3 3 0 0 0 0 0 0 3 3 3 0 0 0 0 0 3 caterpillars) Plulelia M d, Macui nms ustar (diamo h d back moth, paper 2 0 2 2' 2 0 2 3 2 3 2 2 0 0 3 0 2 0 j 0 0 0 0 3 larvae) Phaedon I Cochleariae Mustard] 2 0 0 2 0 l l l 0 2 0 0 0 0 2 2 2 0 0 0 0 l l (mustard beetles) paper Meloidogne a I incognita \Vater l 3 0 3 0 0 0 ,0 v3 0 0 0 3 e nematod es) No. No. of Compound (Table l) -I Su on w of y Pest Species Me ium days 24 25 26 27 28 29 33 34 35 30 37 39 40 4l 'Tetranychustelarius French': g 1 I I (red spider mites, adults) v, Bean 3 3 3 3 3 3 3 l 3 3 2 0 3 g 3 3 3 Tetranychuslelarioux French 1 v (red spider mites; eggs) Bean 3 3 3 3 3i 0,2 0 3 3. ,3- 3 3 .3. 3. Aphisfabae 1 Broad i z t I I 7 (green aphids) .Bean L 2 0 i '0' 0 3' 0 "'0 3 3 2 3 3' -3 3 3 Megoura vic'ea' Broad' v ...:'r:.-..i I "(black aphids) L ,Be'an 2 0- 2 ..0, -0 .3 0 v0 3 3 3 3 3 3 Aederaegypri l v I I u (mosquito larvae) Water l 3 3 '3 0 '3"-'3' 0 3 3: I- 3 3 ".3 3W3 3 Aedesizegypli-- v 3 (mosquito adults) Plywood l 0 0 0 .0 0 0 3 3 3 3 0 TABLE 2-continued No. No. of Compound (Table I) Support of PestSpecies Medium days 1 2 3 4 5 6 7 8 9 10 ll l2 l3 l4 l5 l6 I7 18 19 20 2] 22 Musca domestica Milk/ (houseflies-contacttest*) sugar 2 0 l 0 0 0 0 0 -0 3 3 3 3 2 3 l Musca domestica (houseflies-residualtest*) Plywood 2 0 0 0 0 0 0 0 0 3 3 2 2 O 2 0 Pieris hrassicae (cabbage white caterpillars) Cabbage 2 O 0 0 0 0 0 0 3 3 2 3 0 3 2 Plutella maculipennis Mustard/ (diamond back moth, larvae) paper 2 l 0 O 0 O 0 0 -0 3 3 2 0 3 3 0 Phaedon cochleariae Mustard/ (mustard beetles) paper 2 0 0 O 0 0 0 0 0 3 l 3 3 3 3 0 Meloidogyne incognita nematodes Water 1 O O 0 0 O 0 O 3 3 3 0 O No. Support of No. of Compound (Table 1) Pest Species medium days 42 43 44 45 47 48 49 51 52 54 55 57 58 59 61 Tetmnychus telarius French (red spider mites, adults) Bean 3 3 0 3 0 3 0 3 l 3 0 3 3 3 3 3 Tetranychus relarius French (red spider mites, eggs) Bean 3 3 0 3 0 3 0 3 0 3 0 3 0 3 0 3 Aphis fabae Broad (green aphids) Bean 2 3 0 0 0 3 0 3 3 3 0 3 3 3 3 3 Megoura viceae Broad (black aphids) Bean 2 3 0 O 0 3 O 3 3 O 0 3 3 3 2 0 Aedes aegypti (mosquito larvae) Water I 0 3 2 0 3 3 0 3 0 3 0 3 0 3 Aedes aegypti (mosquito adults) Plywood l 0 0 0 0 3 0 3 0 0 0 3 0 0 .2 0 Musca domestica Milk/ (houseflies-contact test*) Sugar 2 0 1 3 0 0 0 3 0 3 0 3 0 3 O 3 Musca domestica Plywood (houseflies-residualtesfl) 2 0 0 0 0 0 2 0 0 0 3 0 0 0 0 Pien's brassicae (cabbage white caterpillars) Cabbage 2 0 0 0 O 0 3 3 0 0 0 3 0 2 0 3 Plutella maculipennis Musrard/ (diamond back moth, larvae) paper 2 O 0 0 0 0 l 3 0 O 0 0 0 0 0 Phaedan cochleariae Mustard/ (mustard beetles) paper 2 O 0 0 0 0 0 0 0 0 0 0 0 O 0 0 Meloidogyne incngnila Water (nematodes) l 0 3 0 3 In the contact test the flies are sprayed directly; in the residual test the flies are placed on a medium that had previously been treated. Compound No. l6 (Table I) also killed Calamim grunaria (grain weevils) in a similar test. Compound No. demonstrated an antifeeding effect on Pierir bmrsicae larvae. Compound No. 50 showed herbicidal properties in this test.

Compounds Nos. 34 and 35 were also tested at lower concentrations and at S and 250 ppm. respectively gave a complete kill of both organophosphorus compound susceptible and resistant red spiders ('lelmnychus relarius).

EXAMPLE l6 Compounds of the invention were tested for mollus- 60 cicidal activity and details of the tests conducted are as follows.

A weighed sample of the compound under test was dissolved in 0.5 cc. of an ethanol and acetone mixture (50:50 v/v). The solution was diluted with 0.5 cc. water 65 and poured onto a calf feeding pellet in a glass petri dish and the pellet was air dried for 24 hours. The weight of compound used was chosen so that the dried pellet contained 4% by weight of the active ingredient. Two replicates each consisting of a plastic petri dish containing a pellet, 2slugs, and a moistened filter paper to maintain a high relative humidity were used in each test. The dishes were left in the cold room (10C). After 6 days the kill was assessed.

The slugs used were Agriolimax reticulatus (Mull), and they had been starved for 24 hours before the commencement of the tests. The results of the test are set out in Table 3 below.

TABLE 3 EXAMPLE 17 The compounds of this invention were tested against a variety of foliar fungal diseases of plants. The technique employed is to spray the foliage of the undiseased plants with a solution of the test compound and also to drench the soil in which the plants are growing with another solution of the same test compound. All solutions for spraying and drenching contained 0.0l% of the test compound. The plants were then infected with the disease it was desired to control and after a period of days, depending upon the particular disease, the extent of the disease was visually assessed. The results are given in Table 4.a below, wherein the extent of the disease is given in the form of a grading as follows:-

Grading Percentage Amount of Disease 0 61 to I I 26 to 60 2 6 to 25 3' 0 to 5 TABLE 4 Time interval (days) Disease and Plant Disease code letter (Table 4a) TABLE 4a No. of Compound Disease code letter (Table 3) (Table l) B C D N--,--- Q lO\ALfi-- OO IO-U J WM lnoo-ooo-| ooumnunool [rou-NNO I I I I I I I I I L- I I I I I -I I I I I -I I ]Ou:| w| ouawNONt-uwuuuaoonoowwwohloocuwwwwwu w--w| ]w-| w| wwwowwwol I [owwmwoomrol wwmuau wwwwl uamwww| owutouowouwwoowwonooomwwwwwu m lol wl l ooool -Iowo woouooowuooooocfl wwwow -1 EXAMPLE 18 The culture Fusarium culmorum was maintained on 2% malt agar test tube slopes at 20C. Thirteen to seventeen days prior to testing the chemical, the culture was transferred to soil cornmeals, which consisted of 400 grams of 5% maize meal in John Innes seed compost contained in a 2% pint bottle. The cornmeals were plugged with cotton wool and sterilized in an autoclave for 2 hours, before inoculation. Two days prior to testing the chemical, the seeds and the soil were prepared. The soil was prepared by mixing the cornmeals with John lnnes seed compost at the rate of 2 cornmeals to 3 buckets of compost (2 gallon capacity buckets). The seeds were prepared by rolling grams of wheat seeds Lil in a 25% china clay formulation of the chemical (where the chemical was a powder) or a 12.5% china clay formulation (where the chemical was a liquid) at the rate of 1000 ppm weight/weight, eg. 40 milligrams of 25% formulation on 10 grams of seeds. To test the chemical approximately grams of the mixed soil was placed in a fibre pot, twenty seeds were placed on the surface and a further approximate 100 grams were placed on top of the seeds. This was repeated 3 times making four replicates in all. The pots were maintained in the greenhouse between 16C and 20C. After 10 days the number of germinated seeds was recorded and after 17 days the roots were uncovered and the number healthy recorded. These recordings were compared with untreated seeds and seeds treated with mercury (Agrosan) and calculations were made to obtain a grading for disease control. The gradings used were the same as those of the previous Example, and the results are given in Table 5 below.

The culture Rhizoctonia solani was maintained on soil cornmeals, which consisted of 400 grams of 5% maize meal in John Innes seed compost contained in a /1 pint bottle. The cornmeals were plugged with cottonwool and sterlized in an autoclave for 2 hours before inoculation. Nine days prior to testing the chemical, the soil was prepared by mixing the cornmeals with John Innes seed compost at the rate of l cornmeal to 1% buckets of compost (2 gallon capacity buckets). Four days before testing the chemical, it was mixed with 400 grams of soil in a quart bottle at the rate of 100 ppm. weight/weight. Approximately 100 grams of John Innes seed compost was placed in a fibre pot, eight cotton seeds were placed on the surface, and 100 grams of the mixed soil was placed on top of the seeds. This was repeated three times, making four replicates in all. After 13 days the seedlings were assessed for disease. These assessments were compared with untreated seeds and calculations were made to obtain a grading for disease control. The gradings used were the same as those of the previous two examples. Compound No. 7 of Table 1 gave a grading of 3 and Compound No. 29 a grading of 2.

EXAMPLE 20 The activity of the compound of the invention against a wide variety of plant bacterial diseases and fungal post-harvest saprophytic diseases was investigated by in vitro tests as follows. 5 mg. of the compound under test was dissolved or suspended in 10 cc. of acetone and 2 cc. of this solution or suspension was added to 18 cc. of nutrient agar (for the bacterial diseases) or 16 cc. of 2% malt agar (for the fungal diseases) to give a final concentration of 50 parts per million of the compound under test. 2 cc. of a streptomycin preparation containing I units/cc. was added to the malt agar to prevent bacterial contamination of the fungal tests.' The agar preparations were dried overnight in petri compounds of the invention were tested as potential algicide saA mixed algal culture was treated with a quantity of an aqueous suspension of the compound g h r i the followmg f l Y under test so that the culture contained parts per fi $2 gn 1 m a mu 23"? g? million of the compound. The following compounds or;i h e antif ac elrra actlvlt Was assesse a l v ays were found to completelycontrol the algal growth at an t 6 unga actw'ty a ter 6 days this concentration. Compound Nos. 24, 25, 28, 41, 42,

The results of the tests are set out below in Table 7 I0 4 52 58 and 61 (antibacterial activity) and Table 8 (antifungal activity). The results are graded as in Example 16 above.

The names of the disease organisms are indicated in Table 6.

TABLE 6 N 7 l5 EXAMPLE 22 Bacterial Disease Code Fungal disease Code This Example illustrates the herbicidal properties of Organism Table7 Organism 'l able8 the compounds of the present invention. The com- Agmbamrium Nigmspom pounds were ball-milled in water containing a surfacelumifaciens Bl sphaerica Fl active agent sold under the name of Lrssapol and com- 20 prising a condensate of'p-nonylphenol with seven to michiganense B2 vilrophthora F2 Erwinia Amman-a eight molar proportions of ethylene oxide. The ball mmwvvm B4 f F3 milled material was diluted with water to give a spray fg' z'z B5 'ZZZZ F4 composition containing 0.1% of the surface-active Psendamonas Phamopsir agent, and sprayed on to young pot plants of the species Yrmgae 86 F5 listed in Table 9 below (Post-emergence test) The rate Streptomyces Ceratocystis scabies B7 paradoxa F6 of application of the active ingredient was equivalent to Pseudvmonfl B8 Glowsporium l0.pounds per acre and the spray volume 100 gallons 2:331:22? per acre. Damage to the plants was assessed on a scale plraseolicala B9 digitatum F8 of 0 to 3 where 0 represents no effect and 3 represents 'l complete kill. In the same experiment pots of soil were am ylovora B l 0 exrgua F9 Bolrylis sown with seeds of the same plant species and then Flo sprayed with the above spray composition at the rate of ,z lfl r F 10 pounds per acre of active ingredient (Pre-emer- Fumrium gence test). The results are given in Table 9 below.

Caeruleum Fl 2 TABLE 9 No of I I Compound Pre-emergence Post-emergence (Table l) Lettuce To- Wheat -Maize Lettuce To- Wheat Maize I N I mato mato 2 0 0 0 v o 2 z 0 0 3- 0 0 0 0 0 l 0 0 4 0 0 0 0 l 3 0 0 S 3 0 0 0 3 3 0 0 6 3 0 0 o 3 3 0 0 7 0 0- 0 0 3- 3 0 i 0 9 0 0 Q 0 3 3 0 0 14 3 3 o 0 3 3 0 0 l9 0 0' 0 0 2 2 0 0 20 2 0 3 v 0 3 l 2 0 2l 2 O 3 l 2 0 0 0 22 1 .30 0 0 2 0 0 0 I TABLE 7 These results demonstrate that the compounds of this Compound r invention have herbicidal properties, and also that No. Disease Code (Table 6) some compounds have particularly useful selective b 1B3 34 B6 B7 B9 l herbicidal activity against broad-leaved plants.

2 0 2 *0 0 0 0 :0 "0 0 0 The following test illustrates the herbicidal properties 6 3 3 3 3 3 3 3 3 3 3 of ther compounds accord g j 5 compounds were formulated for the test described below by ball milling them in water containing 2% of DlSPERSOL T, (Dispersol T is a registered Trade 7 Mark for a surface active agent comprising methylene l I p dinaphthalenesulphonate).

' j a gb ffggig ji The suspensions so obtained were diluted with water Table I F] "F2 F3 =F4 '-F5' "F6 FWFB" F9 F- F- F12 and sprayed at a rate corresponding to gallons per H acre on to (a) pots of compost which had previously 2 3 0 0 2 0 0 0 0 0 0 0 0 been sown with seeds of lettuce, tomato, wheat and 4l 3 3 3 3 3 3 -3 3 3 3 b oun l f 6 3 3 3 3 3 3 3 3 3 3 3 3 maize (pre emergence test) and y g p lettuce, tomato, wheat and maize growing in pots (post- 

1. AN INSECTIONAL, MITICIDAL FUNGICIDAL OR BACTERIACIDAL COMPOSITION COMPRISING, AS ACTIVE INGREDIENT, AN EFFECTIVE INSELECTICIDAL, MITICIDAL, FUNGICIDAL OR BACTERICIDAL AMOUNT OF A COMPOUND OF THE FORMULA:
 2. A method of combating pests selected from the group consisting of insects, mites, fungi and bacteria which comprises applying to said pests or the locus thereof, an effective insecticidal, miticidal, fungicidal or bactericidal amount of a compound of the formula:
 3. A method according to claim 2 wherein said compound has the formula:
 4. A method according to claim 2 wherein said compound has the formula:
 5. A method according to claim 2 wherein said compound has the formula:
 6. A method of treating plants to render them less susceptible to damage by pests selected from the group consisting of insects, mites, fungi and bacteria, which comprises treating the plants or the seeds, corms, bulbs, tubers, rhizomes, or other propagative parts of the plants, with an effective insecticidal, miticidal, fungicidal or bactericidal amount of a compound of the formula:
 7. A method according to claim 6 wherein said compound has the formula:
 8. A method according to claim 6 wherein said compound has the formula:
 9. A method according to claim 6 wherein said compound has the formula: 